Did you remap the controller in the kodi controller configuration gui?
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In kodi system settings > input there are only three options.
Peripherals
Enable mouse and touch screen support which is on and,
Reset above settings to default. There's no configuration setting for PS3 controller.
If I go to system> libreelec> services I enabled Bluetooth. Then I go to Bluetooth folder and it paired my PS3 controller but there's no feedback from controller. Still controlling kodi from my keyboard.